OH自由基与CO反应的研究

用时间分辨-傅立叶变换红外发射光谱法研究了OH自由基与CO的反应.OH自由基由248 nm的激光光解硝酸得到.在实验中首次观测到了产物CO2的非对称伸缩振动(ν3)的激发态.对CO2发射光谱的拟合结果显示,其振动态的布居在量子数v=2时最大 ,而最高振动量子数达到v=6.由实验得到的CO2振动布居与Schatz等人用全量子化计算该反应的中间物HOCO解离动力学得到的CO2布居结果能很好地吻合.     

Sensitively probing the cofactor redox species and photo-induced electron transfer of wild-type and pheophytin-replaced photosynthetic proteins reconstituted in self-assembled monolayers

An ultrathin, ordered, and packed protein film, consisting of the 2-mercaptoacetic acid (MAA), polydimethyldiallylammonium chloride (PDDA), and wild-type (WT) photosynthetic reaction center (RC; termed as WT-RC) or its pheophytin (Phe)-replaced counterpart (termed as Phe-RC), was fabricated by self-assembling technique onto gold electrode for facilitating the electron transfer (ET) between RC and the electrode surface. Near-infrared (NIR)-visible (Vis) absorption and fluorescence (FL) emission spectra revealed the influence of pigment substitution on the cofactors arrangement and excitation relaxation of the proteins, respectively. Square wave voltammetry (SWV) and photoelectric tests were employed to systematically address the differences between the WT-RC films and mutant ones on the direct and photo-induced ET. The electrochemical results demonstrated that ET initiated by the oxidation of the primary donor (P) was obviously slowed down, and the formed P⁺ had more population as well as more positive redox potential in the Phe-RC films compared with those in the WT ones. The photoelectrochemical results displayed the dramatically enhanced photoelectric performances of the mutant ones, further suggesting the slow-down formation of final charge-separated state in Phe-RC. The functionalized protein films introduced in this paper provided an efficient approach to sensitively probe the redox cofactors and ET differences resulting from only minor changes in pigment arrangement in the pigment–protein complex. The favored ET process observed for the membrane proteins RC was potentially valuable for a deep understanding of the multi-step biological ET process and development of versatile bioelectronic devices.     

The effects of atomic multipole moments obtained by the potential-derived method on hydrogen bonding

A potential-derived atomic multipole method called the cumulative potential-derived atomic multipole method is developed, with which electrostatic atomic multipole moments are derived by fitting the molecular electric potential in a cumulative way. It is applied to the hydrides of N , O , F , S , Cl , and methanol and the hydrogen-bonded dimers formed between them. The relationship between atomic multipole moments and molecular charge distributions is found. The structures calculated with Buckingham's electrostatic model are in good agreement with experiments. The phenomena of nonlinear structures of most H -bonded complexes—the deviations of symmetry axes of electron donors from H bonds—and correct distinguishing between two alternative structures are attributed to atomic dipole and quadrupole moments. Compared with other methods, this method has a quantitative and qualitative advantage and simple algorithm. The main conclusion is that the atomic multipole moments play a substantial role, although a potential-derived charge model was deemed sufficient previously. © 1993 John Wiley & Sons, Inc.     

氯化锂为添加剂制得的疏水聚偏氟乙烯不对称微孔膜的形态结构及其膜蒸馏性能

结合膜的形态结构研究了以 LiCl为添加剂制得的疏水 PVDF膜的膜蒸馏性能。与来用水溶液高分子添加剂制得的PVDF微孔膜相比,膜蒸馏性能有了较大提高,尤其具有更高的截留率。制得的微孔膜的蒸馏通量已接近商品膜的膜蒸馏通量,表明以LiCl为添加剂制得的PVDF疏水微孔膜是一种适用于膜蒸馏的较理想的疏水微孔膜。     

Cl+C2H6→HCl+C2H5反应的准经典轨线研究

用三原子模型的准经典轨线方法研究了Ｃｌ与Ｃ２Ｈ６（ｖ＝０，ｊ）的反应。计算结果表明，反应产物ＨＣｌ的角度分布基本上为各向同性，其振动分布处于基态，与实验结果相一致。对反应轨线的研究表明，该反应为一直接反应，而且反应碰撞在低及高的碰撞参数下的机理不一样，在低碰撞参数下反应碰撞是直接完成的，产物ＨＣｌ以向后散射为主，转动基本上是冷的，但比高碰撞参数下的热。在高的碰撞参数下则生成短寿命的碰撞复合物，产物     

8—氮鸟嘌呤的极谱伏安行为

用循环伏安法（ＣＶ）、电流采样极诸法（ＳＣＰ，即ＴＡＳＴ）、常规脉冲极谱法（ＮＰＰ）、微分脉冲极谱法（ＤＰＰ）、线性扫描伏安法（ＬＳＶ）、Ｏｓｔｅｒｙｏｕｎｇ方波伏安法（ＯＳＷＶ）和计时库仑法（ＣＣ）等电化学技术研究了抗癌药物８－氮鸟嘌呤（８－ａｚａｇｕａｎｉｎｅ，ｇｕａｎａｚｏｌｏ，简称８－ＡＧ）的极谱伏安行为．在 ０． １ｍｏｌ／Ｌ Ｈ２ＳＯ４底液中，８－ＡＧ有一良好的还原峰，峰电位（Ｅｐ）在－０． ９５Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ，下同）附近，８－ＡＧ浓度在４×１０－６～８×１０－４ｍｏｌ／Ｌ范围内．峰高与浓度有良好的线性关系，线性相关系数ｒ＝０．９９９９～０．９９１０，检出限为１× １０－６ｍｏｌ／Ｌ．实验证明了该峰具有吸附性．本文提出了电极反应机理，它包括：酸性介质中８－ＡＧ的质子化、质子化的８－ＡＧ在汞电极上吸附以及完全不可逆的两电子还原过程．同时用量子化学计算方法（全略微分重叠法即ＣＮＤＯ／２）对８－ＡＧ和鸟嘌呤的各原子的净电荷以及Ｗｉｂｅｒｇ键级进行了计算，从理论上解释了８－ＡＧ的电化学还原机理。     

1—酰基—4—氯环己烷与取代芳烃的区域与立体选择性反应

从环己烯合成了１－酰基－４－氯环己烷，发现在其在ＡｌＣｌ３催化与苯，氯苯，溴苯等优先生成反式１－芳基－４－酰基环己烷，与联苯反应时选择性较差。     

三烃基锡肟类化合物的合成及生物活性

共合成了１３个未见文献报道的三烃基锡肟衍生物，测定了它们的＾１ｈ，（＾１３Ｃ，＾１１９Ｓｎ）ＮＭＲ，ＩＲ和ＭＳ。结果表明此类化合物为四配位锡单体结构，生物活性测定结果表明部分化合物同时兼有杀菌、杀螨、除草多种活性。     

二(2,4,4-三甲基戊基)膦酸-上胺205-正庚烷乳状液膜分离钪(Ⅲ)、铁(Ⅲ)和镥(Ⅲ)

本文研究了二（2，4，4-三甲基戊基）膦酸（Cyanex272）-上胺205-正庚烷乳状液膜分离Sc（Ⅲ）、Fe（Ⅲ）和Lu（Ⅲ）。考察了外相酸度、表面活性剂浓度、流动载体浓度及内相盐酸浓度对Sc（Ⅲ）迁移的影响。并探讨了该液膜体系分离Sc（Ⅲ）、Fe（Ⅲ）和Lu（Ⅲ）的可能性，结果表明，该体系对于稀土矿中Sc（Ⅲ）的分离与分析有良好的应用前景。     

ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE

The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here.